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Ukrainian officials did not immediately confirm or deny Russia's claims about the crash in Russia's Belgorod border region yesterday, although they said they were looking into them.
The Associated Press could not confirm who was aboard the plane, and Ukrainian officials cautioned against sharing unverified information.
Throughout the 700-day war, Russia and Ukraine have traded conflicting accusations, and establishing the facts has often been difficult, both because of the constraints of a war zone and because each side tightly controls information.
Footage of the crash posted on social media showed a plane falling from the sky in a snowy, rural area, and a massive ball of fire erupting where it apparently hit the ground.
In addition to the 65 POWs, the Il-76 transport carried a crew of six and three other passengers, the Russian military said. According to the statement, Russian radar registered the launch of two missiles from Ukraine's Kharkiv region that borders the Belgorod region. The ministry did not provide evidence for its claim.
Firefighters, ambulances and police rushed to the site of the crash in the Korochansky district of Belgorod, state news agency Tass said, citing a local emergency services official.
The Russian military said the POWs were being flown to the region for a prisoner swap when the plane was downed at 11.15am (6.15pm AEDT) yesterday.
The Ukrainian military intelligence spokesman, Andrii Yusov, confirmed to media that a prisoner swap was to happen yesterday but was not going ahead. He said the agency is checking whether Ukrainian POWs were on the plane.
The plane was headed to the Belgorod region from the Chkalovsky air field in the Moscow region, and the POW swap was scheduled to take place at the Kolotilovka crossing on the Russian-Ukrainian border, the statement read. The crossing is about 135 kilometres west of the village of Yablonovo, near where the plane fell.
Russian officials and lawmakers expressed outrage and questioned whether there should be further prisoner swaps. The most recent one, brokered by the United Arab Emirates, took place this month and was the biggest to date, with 230 Ukrainian POWs returning home and 248 Russians released. It was the first in almost five months and 49th since the war began.
Ukraine's Kharkiv region and Russia's Belgorod region have long been a focus of the fighting, especially involving airstrikes with missiles and drones.
Russia has largely ensured its air dominance during the war against Ukraine's fleet of Soviet-era warplanes. But Russia has suffered a series of crashes that some observers have attributed to a higher number of flights amid the fighting in Ukraine.
Ukraine defenders 'bending but not breaking' in fierce fighting
At the same time, Kyiv has boasted of shooting down two Russian command and control planes, which would be a major feat for Ukraine if true. Cross-border attacks on Russia's Belgorod region also have increased, with the deadliest one killing 25 people in December.
Shortly before the crash, Vyacheslav Gladkov, Belgorod's governor, said on his Telegram channel that a "missile alert" had been triggered in the region and warned residents to take shelter.
Ukraine's Coordination Headquarters for the Treatment of Prisoners of War said it was looking into the crash but did not immediately provide any information. Instead, it cautioned against sharing "unverified information".
"We emphasise that the enemy is actively conducting information special operations against Ukraine aimed at destabilising Ukrainian society," it said in a statement on Telegram.
A special military commission was on the way to the crash site, according to the Russian Defence Ministry, which said that, in addition to the POWs, three people accompanying them and six crew were on board.
Speaking on his morning call with reporters, President Vladimir Putin's spokesperson Dmitry Peskov said he could not comment on the crash as he did not have enough information about it.
The plane is designed to airlift troops, cargo, military equipment and weapons. It can carry up to 225 troops, according to Russia's military export agency.
Earlier yesterday, Ukrainian President Volodymyr Zelenskyy said a major Russian missile attack that apparently was devised to overwhelm Ukraine's air defences had killed 18 people and injured 130. Ukraine is marking the 700th day since the full-scale invasion by Kremlin's forces started.
The barrage employing more than 40 ballistic, cruise, anti-aircraft and guided missiles early Tuesday hit 130 residential buildings in three Ukrainian cities, "all ordinary houses", Zelenskyy said on X, formerly Twitter.
Russia's onslaught, which included targets in the capital Kyiv and second-largest city Kharkiv, was the heaviest in weeks and lent weight to Zelenskyy's appeals for Western allies to provide more military aid.
"This year, the main priority is to strengthen air defense to protect our cities and towns, as well as defend frontline positions," Zelenskyy said on X late yesterday (early this morning AEDT).
With the 1500-kilometre front line largely static amid icy weather and as both sides seek to replenish their weapons stockpiles, the war recently has focused on long-range strikes.
Analysts say Russia stockpiled missiles to pursue a winter campaign of aerial bombardment, while Ukraine has sought to strike inside Russia with new types of drones.
Russia may have employed decoy missiles in Tuesday's attack in an effort to open up holes in Ukraine's air defences, a US think tank said.
The Washington-based Institute for the Study of War said Moscow is likely trying to acquire more ballistic missiles from foreign countries, including Iran and North Korea, because they may be more effective in some circumstances.
A further barrage of Russian S-300 missiles struck residential districts of Kharkiv late yesterday (early today AEDT), injuring nine people and damaging residential buildings, regional Governor Oleh Syniehubov said.
Russia denies its forces strike civilian areas, although there is substantial evidence to the contrary.
The Russian Defence Ministry said air defences shot down four Ukrainian drones over the Oryol region of western Russia today.
Oryol Mayor Yuri Parakhin said that several drones were downed over the city. He said there were no casualties, but windows were shattered in several apartment buildings in the city.
Another Ukrainian drone was downed today over the Belgorod border region, according to regional Governor Vyacheslav Gladkov. He said there were no casualties or damage.
Ukraine's allies have promised to keep sending military aid packages, even though their resources are stretched. Help from the United States, by far Ukraine's single biggest provider, has also hit political snags.
The German Defense Ministry said Wednesday it plans to send six Sea King Mk41 helicopters to Ukraine.